CN103738912B - Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching - Google Patents
Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching Download PDFInfo
- Publication number
- CN103738912B CN103738912B CN201310733086.4A CN201310733086A CN103738912B CN 103738912 B CN103738912 B CN 103738912B CN 201310733086 A CN201310733086 A CN 201310733086A CN 103738912 B CN103738912 B CN 103738912B
- Authority
- CN
- China
- Prior art keywords
- monocrystalline silicon
- sio
- solution
- probe
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
Based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, be mainly used in the processing of monocrystalline silicon surface nanometer structure.Its concrete operation method is: first grow SiO by the method for wet oxidation at monocrystalline silicon surface
xthin layer, then has SiO by growth
xthe monocrystalline silicon of thin layer takes out and cleans and be fixed on sample stage, then spherical for silica probe is arranged on scanning probe microscopy or the micro-nano process equipment of Multi-contact, starting device, control probe to scan at sample surfaces by the parameter of setting, mixed solution sample being placed in KOH solution and isopropyl alcohol again carries out lithography, can complete.The method SiO used
xmask fabrication simple and easy, with low cost; In probe scanning process, contact is extremely low, can not cause the surrender of monocrystal silicon substrate, processes the monocrystalline silicon nanometer structure service life obtained long; The SiO that wet oxidation obtains
xthin-layer mask function well, can improve working depth.
Description
Technical field
The present invention relates to the nanoprocessing method of monocrystalline silicon surface.
Background technology
Nanosecond science and technology have far-reaching influence for the development of Modern Manufacturing Science technology, and as the basis of device miniaturization, minute manufacturing technology becomes the important directions that manufacturing industry advances, and reflect a national hi-tech development level to a certain extent.And nanometer manufacturing science supports the basis that nanosecond science and technology move towards application.Along with the development of device miniaturization, ultraprecise and microfabrication become the key technology of micro-/nano electromechanical systems (MEMS/NEMS),
Monocrystalline silicon, because of its outstanding mechanical performance and physical property, is widely used in MEMS/NEMS.Monocrystalline silicon processing method conventional is at present faced with the challenges such as low resolution, poor efficiency, complicated operation.Along with the development trend of micro-nano device microminiaturization, current technology is difficult to the requirement of satisfied following micro-nano processing.
In recent years, probe technique, because of its functional diversity, is implemented flexibility and is applied to micro-nano manufacture field gradually.The common probe processing method for monocrystalline silicon generally depends on anodic oxidation or rubbing action, and anodised influence factor is numerous and diverse, and high to the requirement of environment, therefore processing cost is high; And the scan-probe that friction induction method uses is generally the diamond of high rigidity, in process, 5GPa is greater than to substrate applied pressure, inevitably certain damage is caused to monocrystal silicon substrate, thus affect the service life of structure.In addition, " mask " that friction induction is formed generally depends on chemical reaction or malformation, and be somebody's turn to do " mask " densification not, anti-etching ability is poor, also limit the depth/height of institute's processing structure.
Summary of the invention
The object of this invention is to provide a kind of monocrystalline silicon surface non-destructive nano processing method based on tribochemistry induced selective etching, the method, to substrate not damaged, processes the monocrystalline silicon nanometer structure service life obtained long; The depth-width ratio of micro nano structure is large; And it is simple, efficient, accurate.Mask in KOH solution etching process is obtained by wet process oxidation technology, and film-forming method is simple, with low cost.
The present invention is for realizing its goal of the invention, and the technical scheme adopted is, a kind of monocrystalline silicon surface non-destructive nano processing method based on tribochemistry induced selective etching, and its concrete operation step is followed successively by:
A, be the H of 98% by mass concentration
2sO
4solution and mass concentration are the H of 30%
2o
2solution is mixed to get mixed solution by the volume ratio of 7:2-3; Mixed solution is heated to 80-90 DEG C; Again the monocrystalline silicon of HF solution passivation process is placed in mixed solution and processes 25-35 minute, make its surface-borne go out SiO
xthin layer; Then growth there is SiO
xthe monocrystalline silicon of thin layer takes out, and cleans;
B, be that spherical silica probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, starting device, control probe with the contact of 1GPa, according to setting track while scan scan at sample surfaces, make the SiO of scanning area
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 10-25% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:4-6; Monocrystalline silicon after the process of B step is placed in mixed solution and etches 2-60 minute.
Process of the present invention and mechanism as follows: the monocrystalline silicon after HF solution passivation is placed in the H being heated to 90 DEG C by (1)
2sO
4, H
2o
2process in mixed solution (being commonly called as SPM solution), be about the SiO of 2nm at its superficial growth thickness
xthin layer; (2) under atmospheric environment, the SiO of monocrystalline silicon surface
xlayer is removed gradually under the tribochemistry effect of silica probe, for follow-up KOH solution provides etching breach, and then completes processing.Because the method depends on tribochemistry effect, in probe scanning process, contact is far below the critical contact pressure causing monocrystalline silicon that surrender occurs, do not cause the yield deformation of material, the nanometer channel structure obtained remains monocrystalline silicon, therefore is a kind of undamaged nanoprocessing method.
Compared with prior art, the invention has the beneficial effects as follows:
One, the method depends on tribochemistry, and the contact of probe scanning process middle probe and monocrystalline silicon is only 1GPa, and the critical contact pressure (11GPa) surrendered much smaller than causing monocrystalline silicon, therefore can not cause the surrender of material.
Meanwhile, applicant finds at H
2sO
4, H
2o
2the SiO grown in mixed solution
xlayer, when the contact higher than 1GPa, probe can touch monocrystalline silicon surface, causes unnecessary frictional dissipation, and may form non crystalline structure, and the structure of damage monocrystalline silicon, also increases the difficulty of subsequent solution etching; The contact being less than 1GPa can make SiO
xremove abundant not, surface irregularity, the groove structure roughness that subsequent etching obtains is high.And the contact of 1GPa had both been enough to the SiO of scanning area
xthin layer is thoroughly removed, and makes the surface etch behavior of follow-up pure chemistry can obtain the low groove structure of roughness, probes touch can not be made again to monocrystalline silicon surface, avoid frictional dissipation, not cause the change of matrix cystal structure.Therefore the nanostructured not damaged processed.
Two, compared with traditional mask fabrication technique (as thermal oxide, chemical deposition etc.), the present invention carrys out the oxide layer of grown silicon by the method for wet oxidation, and its cost is lower, and film-forming process is simpler and easy.
Three, the KOH solution in etching process and HF solution are easy to obtain, and etching process completes under normal temperature, normal pressure, and only need control etch period can obtain certain etching depth.
Four, the method has departed from mask or the masterplate of fixed structure, and the structure of processing depends on track while scan.And the scanning shape of this method, scanning center can be arranged conveniently by operating system, there is the flexibility of height.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 a is the AFM figure of the monocrystalline silicon surface groove structure that embodiment one processing obtains; Fig. 1 b embodiment one processes the cross-sectional profiles figure of the monocrystalline silicon surface groove structure obtained.
Fig. 2 is the AFM figure of the monocrystalline silicon surface groove structure that embodiment two processing obtains.
Fig. 3 is the AFM figure of the monocrystalline silicon surface groove structure that embodiment three processing obtains.
Fig. 4 is the AFM figure of the monocrystalline silicon surface groove structure that embodiment four processing obtains.
Fig. 5 is the AFM figure of the monocrystalline silicon surface groove structure that embodiment slender acanthopanax work obtains.
Fig. 6 is the AFM figure of the monocrystalline silicon surface groove structure that embodiment six processing obtains.
Fig. 7 a is the AFM figure of the monocrystalline silicon surface groove structure that embodiment seven processing obtains.
Fig. 7 b is the cross-sectional profiles figure of the monocrystalline silicon surface groove structure that embodiment seven processing obtains.
Detailed description of the invention
Embodiment one
Based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, its concrete operation step is followed successively by:
A, be the H of 98% by mass concentration
2sO
4solution and mass concentration are the H of 30%
2o
2solution is mixed to get mixed solution by the volume ratio of 7:3; Mixed solution is heated to 90 DEG C; Again the monocrystalline silicon of HF solution passivation process is placed in mixed solution process 30 minutes, makes its surface-borne go out SiO
xthin layer; Then growth there is SiO
xthe monocrystalline silicon of thin layer takes out, and cleans;
B, be that spherical silica probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, start scanning probe microscopy, control probe with the contact of 1GPa, carry out Surface scan according to the Surface scan tracks of 2 μm × 2 μm at sample surfaces; The SiO of scanning area can be made
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 20% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:5; Again the monocrystalline silicon after the process of B step is placed in mixed solution etching 8 minutes;
Fig. 1 a is the AFM figure that this example processes the monocrystalline silicon surface groove structure obtained; Fig. 1 b is the cross-sectional profiles figure that this example processes the monocrystalline silicon surface groove structure obtained.Fig. 1 a and Fig. 1 b shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is the groove of 200nm.
Embodiment two
Based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, its concrete operation step is followed successively by:
A, be the H of 98% by mass concentration
2sO
4solution and mass concentration are the H of 30%
2o
2solution is mixed to get mixed solution by the volume ratio of 7:3; Mixed solution is heated to 90 DEG C; Again the monocrystalline silicon of HF solution passivation process is placed in mixed solution process 30 minutes, makes its surface-borne go out SiO
xthin layer; Then growth there is SiO
xthe monocrystalline silicon of thin layer takes out, and cleans;
B, be that spherical silica probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, start scanning probe microscopy, control probe with the contact of 1GPa, carry out Surface scan according to the Surface scan tracks of 2 μm × 2 μm at sample surfaces; The SiO of scanning area can be made
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 20% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:5; Monocrystalline silicon after the process of B step is placed in mixed solution etching 2 minutes.
Fig. 2 is the AFM figure that this example processes the monocrystalline silicon surface groove structure obtained, and Fig. 2 shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is the groove of 57nm.
Embodiment three
Based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, its concrete operation step is followed successively by:
A, be the H of 98% by mass concentration
2sO
4solution and mass concentration are the H of 30%
2o
2solution is mixed to get mixed solution by the volume ratio of 7:2; Mixed solution is heated to 80 DEG C; Again the monocrystalline silicon of HF solution passivation process is placed in mixed solution process 25 minutes, makes its surface-borne go out SiO
xthin layer; Then growth there is SiO
xthe monocrystalline silicon of thin layer takes out, and cleans;
B, be that spherical silica probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, start scanning probe microscopy, control probe with the contact of 1GPa, carry out Surface scan according to the Surface scan tracks of 2 μm × 2 μm at sample surfaces; The SiO of scanning area can be made
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 10% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:4; Monocrystalline silicon after the process of B step is placed in mixed solution etching 5 minutes.
Fig. 3 is the AFM figure that this example processes the monocrystalline silicon surface groove structure obtained, and Fig. 3 shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is the groove of 147nm.
Embodiment four
The operation of this example is substantially identical with embodiment two, and different is only that the etch period that C walks changes 8 minutes into.
Fig. 4 is the AFM figure that this example processes the monocrystalline silicon obtained, and Fig. 4 shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is the groove of 218nm.
Embodiment five
The operation of this example is substantially identical with embodiment two, and different is only that the etch period that C walks changes 13 minutes into.
Fig. 5 is the AFM figure that this example processes the monocrystalline silicon surface groove structure obtained, and Fig. 5 shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is the groove of 305nm.
Embodiment six
The operation of this example is substantially identical with embodiment two, and different is only that the etch period that C walks changes 15 minutes into.
Fig. 6 is the groove structure that this example processes the monocrystalline silicon surface obtained, and the degree of depth of groove is 382nm.
Embodiment two to embodiment six shows: along with the increase of etch period, and the degree of depth of groove structure is increasing.Therefore the nanostructured of desired depth can be obtained by controlling etch period.
Embodiment 7
Based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, its concrete operation step is followed successively by:
A, use 98%H
2sO
4solution 30%H
2o
2mixed solution (volume ratio is 7:2.5), be heated to 85 DEG C, the monocrystal silicon sample of HF solution passivation process is placed in mixed solution process 35 minutes, make its superficial growth a layer thickness be about the SiO of 2nm
xlayer;
B, be that spherical silicon dioxide probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, start scanning probe microscopy, control probe with the contact of 1GPa, scan according to the setting track while scan in four 2 μm × 2 μm of Surface scan districts, the SiO in the Surface scan region of four 2 μm × 2 μm can be made
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 25% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:6; Again the monocrystalline silicon after the process of B step is placed in mixed solution etching 60 minutes;
Fig. 7 a is the AFM figure that this example processes the monocrystalline silicon surface groove structure obtained; Fig. 7 b is the cross-sectional profiles figure that this example processes the monocrystalline silicon surface groove structure obtained.Fig. 7 a and Fig. 7 b shows, this example is processed the monocrystalline silicon obtained and defined length and width on its surface and be 2 μm, and the degree of depth is four grooves of 173nm.
Above-described embodiment shows, by parameters such as gated sweep track, scanning load, sweep limits, etch periods, can process various nanostructured at monocrystalline silicon surface, wherein, and working depth and the positive correlation of KOH solution etch period.
Claims (1)
1., based on a monocrystalline silicon surface non-destructive nano processing method for tribochemistry induction etching, its concrete operation step is followed successively by:
A, be the H of 98% by mass concentration
2sO
4solution and mass concentration are the H of 30%
2o
2solution is mixed to get mixed solution by the volume ratio of 7:2-3; Mixed solution is heated to 80-90 DEG C; Again the monocrystalline silicon of HF solution passivation process is placed in mixed solution and processes 25-35 minute, make its surface-borne go out SiO
xthin layer; Then growth there is SiO
xthe monocrystalline silicon of thin layer takes out, and cleans;
B, be that spherical silica probe is arranged on scanning probe microscopy by tip, A is walked the monocrystalline silicon obtained to be fixed on sample stage, starting device, control probe with the contact of 1GPa, according to setting track while scan scan at sample surfaces, make the SiO of scanning area
xthin layer is removed, and substrate exposes;
C, isopropyl alcohol joined mass concentration be in the KOH solution of 10-25% mixed solution, the volume ratio adding fashionable isopropyl alcohol and KOH solution is 1:4-6; Monocrystalline silicon after the process of B step is placed in mixed solution and etches 2-60 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310733086.4A CN103738912B (en) | 2013-12-27 | 2013-12-27 | Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310733086.4A CN103738912B (en) | 2013-12-27 | 2013-12-27 | Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103738912A CN103738912A (en) | 2014-04-23 |
| CN103738912B true CN103738912B (en) | 2016-02-03 |
Family
ID=50496007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310733086.4A Active CN103738912B (en) | 2013-12-27 | 2013-12-27 | Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103738912B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744671A (en) * | 2016-11-30 | 2017-05-31 | 西南交通大学 | A kind of monocrystalline silicon surface nanoprocessing method based on UV ozone |
| CN108821230A (en) * | 2018-06-25 | 2018-11-16 | 西南交通大学 | A kind of lossless micro-nano structure processing method secondarily etched based on anodic oxidation- |
| CN109179314A (en) * | 2018-10-24 | 2019-01-11 | 西南交通大学 | Based on hydrofluoric acid/nitric acid mixed solution friction induction nanoprocessing method |
| CN109850842A (en) * | 2019-03-05 | 2019-06-07 | 西南交通大学 | A kind of lossless processing method of monocrystalline silicon surface nanometer hole |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101086962A (en) * | 2006-03-13 | 2007-12-12 | 香港科技大学 | Metal-induced crystallization of amorphous silicon |
| CN101549853A (en) * | 2009-05-13 | 2009-10-07 | 西南交通大学 | Processing method for constructing nano projection structure on surface of single crystal silicon based on friction induction |
| CN102020239A (en) * | 2009-09-09 | 2011-04-20 | 中国科学院金属研究所 | Patterning growth method of single-walled carbon nanotubes by surface ruling method |
| JP4700119B2 (en) * | 2009-03-19 | 2011-06-15 | エスアイアイ・ナノテクノロジー株式会社 | Microfabrication method using atomic force microscope |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09289192A (en) * | 1996-04-23 | 1997-11-04 | Nippon Steel Corp | Working pin for fine working of semiconductor substrate and fine working method of semiconductor substrate |
| JP2007320017A (en) * | 2006-06-05 | 2007-12-13 | Sii Nanotechnology Inc | Working method using atomic force microscope fine working device |
-
2013
- 2013-12-27 CN CN201310733086.4A patent/CN103738912B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101086962A (en) * | 2006-03-13 | 2007-12-12 | 香港科技大学 | Metal-induced crystallization of amorphous silicon |
| JP4700119B2 (en) * | 2009-03-19 | 2011-06-15 | エスアイアイ・ナノテクノロジー株式会社 | Microfabrication method using atomic force microscope |
| CN101549853A (en) * | 2009-05-13 | 2009-10-07 | 西南交通大学 | Processing method for constructing nano projection structure on surface of single crystal silicon based on friction induction |
| CN102020239A (en) * | 2009-09-09 | 2011-04-20 | 中国科学院金属研究所 | Patterning growth method of single-walled carbon nanotubes by surface ruling method |
Non-Patent Citations (1)
| Title |
|---|
| "Maskless and low-destructive nanofabrication on quartz by friction-induced selective etching";Chenfei Song et al.;《Nanoscale Research Letters》;20130327;第8卷;第2页方法部分，图1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103738912A (en) | 2014-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103738912B (en) | Based on the monocrystalline silicon surface non-destructive nano processing method of tribochemistry induction etching | |
| Yang et al. | Effects of mechanical agitation and surfactant additive on silicon anisotropic etching in alkaline KOH solution | |
| Persson et al. | Double thermal oxidation scheme for the fabrication of SiO2 nanochannels | |
| US20020031321A1 (en) | Low-loss waveguide and method of making same | |
| CN103803484B (en) | Based on the silicon nitride film/silicon micro-nano processing method of friction induction selective etch | |
| CN102792419A (en) | Process and structure for high temperature selective fusion bonding | |
| CN103030106B (en) | Three-dimensional nanometer structure array | |
| CN1749153A (en) | Method for producing MEMS sensor suspension beam structure | |
| CN1313357C (en) | Integration manufacturing method of cantilever beam type dot needle-point based on silicon oxide film | |
| WO2008090428A1 (en) | Surface roughening process | |
| CN103193197B (en) | A kind of micro element movable structure preparation method based on silicon/glass anode linkage | |
| CN106744671A (en) | A kind of monocrystalline silicon surface nanoprocessing method based on UV ozone | |
| CN106610439B (en) | Tilting silicon needle point and preparation method thereof | |
| Lee et al. | Silicon profile transformation and sidewall roughness reduction using hydrogen annealing | |
| CN106567131A (en) | Machining method for pinpoints on surface of monocrystalline silicon based on indentation induced selective etching | |
| JP2010131734A (en) | Method for manufacturing silicon microstructure and method for manufacturing microchannel device | |
| Fulong et al. | Micro-fabrication of crystalline silicon by controlled alkali etching | |
| Lee et al. | Method on surface roughness modification to alleviate stiction of microstructures | |
| Saito et al. | Fabrication of micro-structure on glass surface using micro-indentation and wet etching process | |
| CN101695992B (en) | Method for manufacturing electric heating drive micro-clamp based on body silicon processing technique | |
| Rao et al. | High speed silicon wet bulk micromachining of Si {111} in KOH based solution | |
| CN117805443A (en) | Preparation method of atomic force probe | |
| JP2003329567A (en) | Method of producing spm sensor | |
| CN109850842A (en) | A kind of lossless processing method of monocrystalline silicon surface nanometer hole | |
| Peng et al. | Combined AFM nano-machining and reactive ion etching to fabricate high aspect ratio structures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |